Recording liquid and image recording method

ABSTRACT

A recording liquid including a colorant, water and at least two kinds of fine resin particles. In a preferred embodiment, at least one of the two kinds of the fine resin particles are fine self-crosslinkable resin particles. In another preferred embodiment, the number of the kinds of the fine resin particles is 3 or more. Also, disclosed is an image recording method using the recording liquid.

This appl. is a divisional of U.S. appl. Ser. No. 08/925,391, filed Sep.8, 1997 now U.S. Pat. No. 6,075,085.

FIELD OF THE INVENTION

The present invention relates to a recording liquid and an imagerecording method, and more particularly to a recording liquid comprisinga colorant, water and fine resin particles, and an image recordingmethod using the same.

BACKGROUND OF THE INVENTION

Recently, attentions have been paid to ink jet systems, i.e., imagerecording methods in which droplets of recording liquids are dischargedfrom recording heads to record images on recording media, because therunning cost thereof is low and this system can be easily applied tocolor image system for output devices of information instruments such ascomputers. As recording liquids for ink jet printers, aqueous solutionsof dyes which are mainly composed of water and dyes have hitherto beenused. However, there is the problem that when recording liquids jettedfrom nozzles adhere to recording paper, they blurred on the recordingpaper so that the resulting dot images become extremely larger dropletsformed by jetting, or have low image density, to thereby result in lowimage quality. Further, there is the problem that the images are easilyblurred or flow with water, because of low water resistance of therecorded images. Furthermore, there is the problem that the images areeasily faded by irradiation of light such as sunlight, because of lowlight resistance.

As to recording liquids for ink jet printers, techniques have beenproposed in which film-forming fine resin particles are added torecording liquids to solve the above described problems of the aqueoussolutions of dyes. For example, JP-B-60-32663 (the term “JP-B” as usedherein means an “examined Japanese patent publication”) discloses arecording liquid to which a latex is added as the fine resin particles,JP-A-5-239392 (the term “JP-A” as used herein means an “unexaminedpublished Japanese patent application) discloses a recording liquid towhich a water-dispersible resin having carboxyl and nonionic hydrophilicgroups is added, JP-A-5-255628 discloses a recording liquid to which avinyl polymer of a non-crosslinked structure, and JP-A-6-340835discloses a recording liquid to which polyester particles having ionicgroups are added. Further, JP-B-7-47355 discloses a technique whichcomprises adding particles of a resin such as a polyester and acrosslinking agent to a recording liquid, and crosslinking the resin ona recording medium.

However, in all of the recording liquids disclosed in the abovedescribed patents, film formation of the fine resin particles isinitiated at discharge outlet sections of recording heads as watercontained in the recording liquids is evaporated by contacting with air.This results in occurrence of clogging. It has been therefore impossibleto stably discharge the recording liquids. Further, according to theserecording liquids, it has been impossible to completely prevent therecording liquids from blurring in fibers of recording paper bycapillary action, to thereby fail to provide images of high imagequality. Furthermore, it has been impossible to completely prevent theserecording liquids from penetrating into the inside of the recordingpaper, which imposes a limitation on the acquisition of images of highdensity and high image quality. Similarly, there is also a limitation onwater resistance. Moreover, the dilution of the above describedconventional recording liquids with water for avoiding the clogging atdischarge outlets decreases the content of fine resin particlescontained in the same volume of droplets, namely the content of resinsolids contributing to image formation, as compared to that prior to thedilution, which causes a remarkable reduction in image density. It hasbeen therefore impossible to provide images of high image quality. Thatis, in the conventional recording liquids, the provision of imageshaving a high image density and high image quality by increasing thecontent of fine resin particles (the content of resin solids) has beenincompatible with the avoidance of the clogging at discharge outlets.

SUMMARY OF THE INVENTION

The present invention has been made for solving the above describedproblems, and an object of the present invention is to provide arecording liquid which can provide an image having a high image density,exhibiting no blurring on recording paper and no penetration therein,and having excellent water resistance, and which is excellent indischarge stability.

Another object of the present invention is to provide an image recordingmethod using the recording liquid.

Other objects and effects of the present invention will become apparentfrom the following description.

The above described objects of the present invention has been achievedby providing a recording liquid comprising a colorant, water and atleast two kinds of fine resin particles.

In a first preferred embodiment, the recording liquid comprises acolorant, water and at least two kinds of fine resin particles, whereinat least one kind of the at least two kinds of fine resin particles arefine self-crosslinkable resin particles.

In a second preferred embodiment, the recording liquid comprises acolorant, water and at least three kinds of fine resin particles.

The present invention also relates to an image recording methodcomprising discharging droplets of the above described recording liquidfrom a recording head to record an image on a recording medium.

DETAILED DESCRIPTION OF THE INVENTION

The reason why the recording liquids as described above allows theattainment of high image density by increasing the content of fine resinparticles (the content of resin solids) to be compatible with theavoidance of the clogging at a discharge outlet of a recording head isnot fully clarified, but inferred as follows.

The inclusion of at least two different kinds of fine resin particles inthe recording liquid decreases the probability that around (at proximatecoordinate positions) a certain fine resin particle is present a fineresin particle of the same kind as this fine resin particle. Thisdecreases the probability that the fine resin particles of the same kindcome close to and collide with each other, which inhibits a series ofprocesses from the approach of the fine resin particles of the same kindto each other to film formation through their collision and fusion(coordination effect), resulting in prevention of clogging.

Similarly, the inclusion of at least three different kinds of fine resinparticles in the recording liquid decreases the probability that around(at proximate coordinate positions) a certain fine resin particle ispresent a fine resin particle of the same kind as the fine resinparticle to one third or less. This decreases the probability that thefine resin particles of the same kind come close to and collide witheach other, which inhibits a series of processes from the approach ofthe fine resin particles of the same kind to each other to filmformation through their collision and fusion (coordination effect),resulting in prevention of clogging.

Further, the attraction between particles becomes more difficult to actwhen different kinds of fine resin particles are present in therecording liquid than when only fine resin particles of the same kindare present (the repulsion becomes easy to act). Accordingly, fine resinparticles of the same kind are prevented from coming close to eachother, and the probability of their collision is decreased (the effectof repulsion between particles). Similar to the above, therefore, aseries of processes from the approach of the fine resin particles of thesame kind to each other to film formation through their collision andfusion is inhibited, resulting in prevention of the clogging.

Furthermore, with respect to the prevention of the clogging, it isconsidered that the differences in particle size and form between thedifferent kinds of fine resin particles are larger than those betweenthe fine resin particles of the same kind. When around a certain fineresin particle is present a different kind of fine resin particlelargely different therefrom in particle size and form, the fine resinparticles of the same kind and the different kinds are prevented fromcoming close to each other (geometrical structure effect), thereby alsopossibly preventing the clogging as similar to the above.

In the present invention, the fine resin particles are remarkablyprevented from coming close to each other by the sum of the abovedescribed effects, so that the total content of the fine resin particlescontained in the recording liquid can be increased. The content of thefine resin particles in one droplet can also be increased as well whichmakes it possible to form images of high image density.

In addition, images can be rapidly formed on the recording paper by thehigh-speed film-forming property of fine self-crosslinkable resinparticles contained in the recording liquid. That is, the crosslinkingreaction of the fine self-crosslinkable resin particles proceeds at highspeed with evaporation of water contained in droplets of the recordingliquid and penetration of the recording liquid in the paper fromimmediately after adhesion of the droplets of the recording liquidjetted from the recording head to the recording paper, thereby rapidlyforming a firm image film in which the colorant is enclosed in theresin. At this time, in the first preferred embodiment, the filmformation of other coexistent fine self-crosslinkable resin particlesand fine resin particles other than the fine self-crosslinkable resinparticles also proceeds. In the second preferred embodiment, the filmformation of the three or more kinds of fine resin particles proceedsside by side. This prevents the recording liquid from blurring andpenetrating. Thus, it becomes possible to form images comprising resinsand a colorant enclosed therein, and having a high image density andhigh water resistance, on the recording medium such as paper.

The present invention is described in detail below.

The recording liquid of the first preferred embodiment of the presentinvention comprises a colorant, water and at least two kinds of fineresin particles in which fine resin particles of at least one kind arefine self-crosslinkable resin particles.

The term “self-crosslinkable resin” as used in the present inventionmeans a resin which crosslinks by the reactivity of functional groupsincorporated into a main chain and/or side chains of the resin, not bythe action of a crosslinking agent. Examples of such fineself-crosslinkable resin particles include fine acrylsilicone resinparticles and fine acrylamide resin particles. Of these, fineacrylsilicone resin particles containing an alkoxysilyl group arepreferred which can rapidly form firm siloxane crosslinked films withcolorants enclosed therein, from the viewpoints of the high-speedfilm-forming property suitable for rapid image formation and thestrength of the formed films. In the alkoxysilyl group of the finealkoxysilyl group-containing acrylsilicone resin particles, the alkylgroup is preferably alkyl having 1 to 3 carbon atoms, and morepreferably alkyl having 1 or 2 carbon atoms. The acrylic skeletonsinclude, for example, polymers and copolymers of styrene, vinyltoluene,methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutylmethacrylate, 2-ethylhexyl methacrylate, vinyl acetate, acrylonitrile,methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexylacrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate,hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, acrylamide,N-methylolacrylamide and glycidyl methacrylate.

The fine resin particles which can be used together with the abovedescribed fine self-crosslinkable resin particles include finenon-crosslinkable resin particles and fine resin particles crosslinkableby the action of crosslinking agents. Specifically, they include finefluororesin particles, fine acrylic resin particles, fine polyesterresin particles, fine vinyl acetate resin particles, fine vinyl chlorideresin particles, fine styrene-butadiene copolymer resin particles, finepolyurethane resin particles, fine polystyrene resin particles, finevinyl acetate-acrylic copolymer resin particles, vinylacetate-acrylamide copolymer resin particles, ethylene-vinyl acetatecopolymer resin particles, fine epoxy resin particles, fine polyamideresin particles and fine silicone resin particles.

In this embodiment, the fine resin particles contained in the recordingliquids may be composed of the fine self-crosslinkable resin particles,or the fine self-crosslinkable resin particles and the finenon-crosslinkable resin particles and/or the fine resin particlescrosslinkable by the action of crosslinking agents. However, the fineresin particles are preferably composed of the fine self-crosslinkableresin particles and the fine non-crosslinkable resin particles, from theviewpoint of making it difficult to form films by the time differencebetween film formation processes of the respective resins and by thecomposition difference, to thereby prevent clogging, namely, filmformation at discharge outlets of recording heads. Of the finenon-crosslinkable resin particles enumerated, fine fluororesin particlesare preferred, because they are excellent in the film-forming property(image forming property), have high water repellency, high waterresistance and high weather resistance, and are useful for formingimages having high water resistance and a high image density. As thefine fluororesin particles, fine fluororesin particles havingfluoroolefin units are preferred. Fine fluorine-containing vinyl etherresin particles composed of fluoroolefin units and vinyl ether units areparticularly preferred among others.

Examples of the fluoroolefin units include —CF₂CF₂—, —CF₂CF(CF₃)— and—CF₂CFCl—. On the other hand, examples of the vinyl ether units includethose shown below.

As the fine fluorine-containing vinyl ether resin particles composed offluoroolefin units and vinyl ether units, alternating copolymers arepreferred in which the above described fluoroolefin units and vinylether units are alternately combined.

The recording liquid according to the first preferred embodiment of thepresent invention contains at least two kinds of fine resin particlesincluding fine self-crosslinkable resin particles. This sufficientlyallows the attainment of high image density and high image quality bythe increase of the resin solids content to be compatible with theavoidance of clogging. However, when the recording liquid contains threeor more kinds of fine resin particles including fine self-crosslinkableresin particles, the above described probability that fine resinparticles of the same kind are present at proximate coordinate positionsis further decreased (enhancement of the coordination effect), and theattraction between particles becomes more difficult to act. Accordingly,the clogging can be more effectively prevented. There is no particularlimitation on the upper limit with respect to the number of the kinds offine resin particles contained in the recording liquid. However, when itis assumed that the shape and size of each fine resin particle areconstant and that the shape is spherical, the proximate particle number(coordinate number) in the state where the particles are filled mostdensely, namely the number of particles existing in contact with acertain particle, amounts 12. Accordingly, the optimum value of theupper limit number of the kinds of fine resin particles is considered tobe 12. Further considering the width of probabilistic deviation, theupper limit number of the kinds of fine resin particles is preferably 18(12 kinds +6 kinds). From the above, the number of the kinds of fineresin particles contained in the recording liquid according to the firstpreferred embodiment of the present invention is preferably 2 to 18, andmore preferably 3 to 12, from the viewpoints of the approach of the fineresin particles of the same kind to each other by the coordinationeffect and a decrease in collision probability. In the presentinvention, fine resin particles different in at least one of thecharacteristics of the fine resin particles or a dispersion thereof,namely, lowest film-forming temperature, glass transition temperature,ionicity, pH, weight average molecular weight and average particle size,caused by the difference in a modifying method, are considered to fineresin particles of another kind, even if the resin is composed of thesame monomer.

The average particle size of the respective fine resin particles for usein the first preferred embodiment of the present invention is preferably0.01 μm to 5 μm, and more preferably 0.05 μm to 3 μm. The fine resinparticles having an average particle size of less than 0.01 μm aredeteriorated in the film-forming property, whereas exceeding 5 μmresults in lowered optical density (image density).

In the first preferred embodiment of the present invention, the totalcontent of the fine resin particles (the total of the resin solidcontent) is preferably 10 to 95% by weight, more preferably 15 to 90% byweight, and most preferably 20 to 80% by weight, based on the weight ofthe recording liquid. The fine resin particles having a total content ofless than 10% by weight are lowered in image optical density, whereasexceeding 95% by weight raises a fear of lowered discharge stability.Further, when two kinds of fine resin particles are used, the content ofthe fine self-crosslinkable resin particles contained in the recordingliquid preferably ranges from 0.05 W parts by weight to 0.9 W parts byweight, taking the total solid content of the fine resin particles as Wparts by weight. Furthermore, when three or more kinds of fine resinparticles are used, the content of the respective fine resin particlescontained in the recording liquid can be appropriately selected so as torealize desired characteristics at maximum. When n kinds (n: a positiveinteger of 3 or more) of fine resin particles are mixed, the solidcontent of the respective fine resin particles contained in therecording liquid is preferably within the range of 0.1 W/n parts byweight to 2 W/n parts by weight, taking the total solid content of thefine resin particles contained in the recording liquid as W parts byweight. If the content is less or more than this range, the effect ofpreventing the clogging by coexistence of two or more different kinds offine resin particles may be reduced. Furthermore, of the fine resinparticles contained in the recording liquid, the content of the fineself-crosslinkable resin particles is preferably within the range of 0.1W/n parts by weight to 2 W/n parts by weight as similar to the above,and more preferably 0.4 W/n parts by weight to 2 W/n parts by weight,per one kind thereof. If the content is more than 2 W/n parts by weight,the effect of preventing the clogging by coexistence of two or moredifferent kinds of fine resin particles is reduced as described above.On the other hand, if the content is less than 0.4 W/n parts by weight,the image formation speed on paper is decreased to arise a fear oflowered image density.

In the second preferred embodiment, the recording liquid of the presentinvention comprises a colorant, water and at least three kinds of fineresin particles.

The fine resin particles for use in the second embodiment of the presentinvention include fine non-crosslinkable resin particles, fineself-crosslinkable resin particles and fine resin particlescrosslinkable by the action of crosslinking agents. Specifically, fineresin particles such as fine fluorine resin particles, fine polyesterresin particles, fine vinyl acetate resin particles, fine vinyl chlorideresin particles, fine styrene-butadiene copolymer resin particles, finepolyurethane resin particles, fine polystyrene resin particles, finevinyl acetate-acrylic copolymer resin particles, vinylacetate-acrylamide copolymer resin particles, ethylene-vinyl acetatecopolymer resin particles, fine epoxy resin particles, fine polyamideresin particles, fine silicone resin particles, fine acrylic resinparticles and fine acrylsilicone resin particles can be used. The term“self-crosslinkable resin” as used in the present invention means aresin which crosslinks by the reactivity of functional groupsincorporated into a main chain and/or side chains of the resin, not bythe action of a crosslinking agent.

In the second embodiment of the present invention, of the three or morekinds of fine resin particles contained in the recording liquid, atleast one kind of fine resin particles are preferably the finenon-crosslinkable resin particles, from the viewpoint of making itdifficult to form films by the time difference between film formationprocesses of the respective resins and by the composition difference, tothereby prevent clogging, namely, film formation at discharge outlets ofrecording heads. Of the fine non-crosslinkable resin particlesenumerated, fine fluorine resin particles are preferred, because theyare excellent in the film-forming property (image forming property),have high water repellency, high water resistance and high weatherresistance, and are useful for forming images having high waterresistance and a high image density. As the fine fluororesin particles,fine fluororesin particles having fluoroolefin units are preferred. Finefluorine-containing vinyl ether resin particles composed of fluoroolefinunits and vinyl ether units are particularly preferred among others.

Examples of the fluoroolefin units include —CF₂CF₂—, —CF₂CF(CF₃)— and—CF₂CFCl—. On the other hand, examples of the vinyl ether units includethose shown below:

As the fine fluorine-containing vinyl ether resin particles composed offluoroolefin units and vinyl ether units alternating copolymers arepreferred in which the above described fluoroolefin units and vinylether units are alternately combined.

The recording liquid according to the second preferred embodiment of thepresent invention contains at least three kinds of fine resin particles.This sufficiently allows the attainment of high image density and highimage quality by the increase of the content of resin solids to becompatible with the avoidance of clogging. However, when the recordingliquid contains four or more kinds of fine resin. particles, theprobability that fine resin particles of the same kind are present atthe above described proximate coordinate positions is further decreased(enhancement of the coordination effect), and the attraction betweenparticles becomes more difficult to act. Accordingly, the clogging canbe more effectively prevented. There is no particular limitation on theupper limit with respect to the number of the kinds of fine resinparticles contained in the recording liquid. However, when it is assumedthat the shape and size of each fine resin particle are constant andthat the shape is spherical, the proximate particle number (coordinatenumber) in the state where the particles are filled most densely, namelythe number of particles existing in contact with a certain particle,amounts 12. Accordingly, the optimum value of the upper limit number ofthe kinds of fine resin particles is considered to be 12. Furtherconsidering the width of probabilistic deviation, the upper limit numberof the kinds of fine resin particles is preferably 18 (12 kinds+6kinds). From the above, the number of the kinds of fine resin particlescontained in the recording liquid according to the second preferredembodiment of the present invention is preferably 3 to 18, and morepreferably 4 to 12, from the viewpoints of the approach of the fineresin particles of the same kind to each other by the coordinationeffect and a decrease in collision probability. In the presentinvention, fine resin particles different in at least one of thecharacteristics of the fine resin particles or a dispersion thereof,namely, lowest film-forming temperature, glass transition temperature,ionicity, pH, weight average molecular weight and average particle size,caused by the difference in a modifying method, are considered to fineresin particles of another kind, even if the resin is composed of thesame monomer.

The average particle size of the respective fine resin particles for usein the second preferred embodiment of the present invention ispreferably 0.01 μm to 5 μm, and more preferably 0.05 μm to 3 μm. Thefine resin particles having an average particle size of less than 0.01μm are deteriorated in the film-forming property, whereas exceeding 5 μmresults in lowered optical density (image density).

In the second preferred embodiment of the present invention, the totalcontent of the fine resin particles (the total of the resin solidcontent) is preferably 10 to 95% by weight, more preferably 15 to 90% byweight, and most preferably 20 to 80% by weight, based on the weight ofthe recording liquid. The fine resin particles having a total content ofless than 10% by weight are lowered in image optical density, whereasexceeding 95% by weight raises a fear of lowered discharge stability.Further, the content of the respective fine resin particles contained inthe recording liquid can be appropriately selected so as to realizedesired characteristics at maximum. When n kinds (n: a positive integerof 3 or more) of fine resin particles are mixed, the solid content ofthe respective fine resin particles contained in the recording liquid ispreferably within the range of 0.1 W/n parts by weight to 2 W/n parts byweight, taking the total solid content of the fine resin particlescontained in the recording liquid as W parts by weight. If the contentis less or more than this range, the effect of preventing clogging bycoexistence of three or more different kinds of fine resin particles maybe reduced. Further, of the fine resin particles contained in therecording liquid, the content of the fine non-crosslinkable resinparticles is preferably within the range of 0.1 W/n parts by weight to 2W/n parts by weight as similar to the above, and more preferably 0.3 W/nparts by weight to 2 W/n parts by weight, per one kind thereof. If thecontent is more than 2 W/n parts by weight, the effect of preventingclogging by coexistence of three or more different kinds of fine resinparticles is reduced as described above. On the other hand, if thecontent is less than 0.3 W/n parts by weight, there is a fear of reducedwater resistance, as well as lowered clogging prevention effect.

In the present invention, the colorant preferably has a good affinityfor water, i.e., a main solvent in the recording liquids of the presentinvention, or has a good uniform dispersibility. Specifically, pigments,water-soluble dyes and disperse dyes are used.

The pigments for use in the present invention include organic dyes andinorganic dyes. Examples of the pigments for black-and-white imagesinclude carbon black (C. I. Pigment Black 7) such as furnace black andchannel black, and organic pigments such as aniline black (C. I. PigmentBlack 1). Further, the pigments for color images include pigments suchas C. I. Pigment Yellows 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42, 53,55, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 138 and153, C. I. Pigment Violets 1, 3, 5:1, 16, 19, 23 and 38, and C. I.Pigment Blues 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16. The contentof the pigments contained in the recording liquid is preferably 1 to 50%by weight, and more preferably 1.5 to 40% by weight. In order todisperse these pigments more uniformly, they may be dispersed in a ballmill or the like as needed.

The water-soluble dyes for use in the present invention include directdyes and acid dyes. Examples thereof include, but are not limited to, C.I. Direct Blacks 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97,108, 112, 113, 114, 117, 118, 121, 122, 125, 132, 146, 154, 166, 168,173 and 199, C. I. Direct Violets 7, 9, 47, 48, 51, 66, 90, 93, 94, 95,98, 100 and 101, C. I. Direct Yellows 8, 9, 11, 12, 27, 28, 29, 33, 35,39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108,109, 110, 130, 132, 144, 161 and 163, C. I. Direct Blues 1, 10, 15, 22,25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 201, 202,244, 251 and 280, C. I. Acid Blacks 7, 24, 29 and 48, C. I. Acid Violets5, 34, 43, 47, 48, 90 and 103, C. I. Acid Yellows 17, 19, 23, 25, 39,40, 44, 49, 50, 61, 110, 174 and 218, and C. I. Acid Blues 9, 25, 40,41, 62, 72, 76, 80, 106, 112, 120, 205, 230, 271 and 280. The content ofthese dyes contained in the recording liquid is determined depending onthe kind of dye, the kind of solvent component, characteristics requiredfor the recording liquid, and the like. In general, however, it ispreferably within the range of 0.2 to 40% by weight, and more preferablywithin the range of 0.5 to 30% by weight based on the weight of therecording liquid.

Preferred examples of water used in the present invention includeion-exchanged water, ultrapure water, distilled water and ultrafiltratedwater.

In addition, pH adjustors such as potassium dihydrogenphosphate andsodium dihydrogenphosphate, and benzoic acid, dichlorophene,hexachlorophene and sorbic acid for antifungal, preservative and rustpreventive purposes may be added to the recording liquid as needed.Furthermore, various general additives such as ethylene glycol andglycerine may be added to the recording liquid as needed.

The recording liquid of the present invention can be used in an imagerecording method comprising discharging droplets of the recording liquidfrom a recording head to record an image on a recording medium.

Further, the recording liquid of the present invention can beappropriately used not only for the above described ink jet recording,but also for image recording of the electrostatic attraction system andwriting things.

The present invention will be described in more detail below withreference to the following Examples, but the invention should not beconstrued as being limited thereto.

EXAMPLE 1-1

A recording liquid was prepared as follows. Thirty-three parts by weightof an aqueous dispersion of a copper phthalocyanine pigment (PigmentBlue 15:3) (solid content: 35%), 39 parts by weight of a resindispersion containing water and fine acrylsilicone resin particles(average particle size: 0.1 μm to 0.2 μm) having methoxysilyl groups(solid content: 35%, trade name: SW-135, manufactured by Sanyo ChemicalIndustries, Ltd.), and 28 parts by weight of a resin dispersioncontaining water and fine fluorine-containing vinyl ether resinparticles (average particle size: 0.15 μm) prepared by emulsionpolymerization of fluoroolefin and vinyl ether monomers (solid content:50%, trade name: FE-3000, manufactured by Asahi Glass Co., Ltd.) wereuniformly mixed by stirring. Then, the resulting mixed liquid wasfiltered through a membrane filter having a pore size of 10 μm to removedust and coarse particles, to thereby obtain the recording liquid havinga pigment (colorant) concentration in the recording liquid {(the pigmentsolid amount×100)/the total amount of the recording liquid} of 12% byweight, a pigment (colorant) concentration in the solids {(the pigmentsolid amount×100)/the sum of the pigment solid amount and the totalamounts of fine resin particle solids} of 30% by weight, and aconcentration of the total amount of the fine resin particle solids inthe recording liquid {(the total amount of the fine resin particlesolids×100)/the total amount of the recording liquid} of 28% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.7.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

On the other hand, clogging with the recording liquid at a dischargeoutlet of a recording head was evaluated in the following manner. Astandard injection needle having an inner diameter of 180 μm(manufactured by Iwashita Engineering Co.) was set on a tip of aninjector having an inner diameter of 15 mm, and 10 ml of the recordingliquid was sucked in this injector. Then, the injector was allowed tostand in a state in which dropping of the recording liquid from theneedle was stopped by sealing an upper portion of the injector. After anelapse of a specified time, the upper portion was opened, and it wasobserved whether the recording liquid could be continuously dropped fromthe needle. This operation was repeated while prolonging the specifiedtime of standing little by little, and the longest time of standinguntil which the recording liquid could be dropped from the needle wastaken as the allowance time until development of the clogging. Accordingto this system, the thus-measured allowance time until development ofthe clogging with the recording liquid was as long as 40 seconds.

Then, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Further, water was spilled on the above described solid image formedwith a bar coater and the print sample obtained by use of the printer toevaluate the water resistance. As a result, blurring of the image andextension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-2

Twenty-eight parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 33parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), and 39 parts by weightof a resin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 30%, trade name: A-215G, manufacturedby Takamatsu Yushi Co.) were uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 11% by weight, a pigment (colorant)concentration in the solids of 30% by weight, and a concentration of thetotal solids of the fine resin particles in the recording liquid of 23%by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 45 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-3

Thirty-two parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 38parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), and 30 parts by weightof a resin dispersion containing water and fine silicon-modified acrylicresin particles (average particle size: 0.1 μm to 0.2 μm) (solidcontent: 45%, trade name: G-45, manufactured by Sanyo ChemicalIndustries, Ltd.) were uniformly mixed by stirring. Then, the resultingmixed liquid was filtered through a membrane filter having a pore sizeof 10 μm to remove dust and coarse particles, to thereby obtain arecording liquid having a pigment (colorant) concentration in therecording liquid of 11% by weight, a pigment (colorant) concentration inthe solids of 30% by weight, and a concentration of the total solids ofthe fine resin particles in the recording liquid of 27% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 40 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example was high in waterresistance.

EXAMPLE 1-4

Thirty-four parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 27parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), 19 parts by weight ofa resin dispersion containing water and fine fluorine-containing vinylether resin particles (average particle size: 0.15 μm) prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers (solidcontent: 50%, trade name: FE-3000, manufactured by Asahi Glass Co.,Ltd.), and 21 parts by weight of a resin dispersion containing water andfine silicon-modified acrylic resin particles (average particle size:0.1 μm to 0.2 μm) (solid content: 45%, trade name: G-45, manufactured bySanyo Chemical Industries, Ltd.) were uniformly mixed by stirring. Then,the resulting mixed liquid was filtered through a membrane filter havinga pore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 12% by weight, a pigment (colorant)concentration in the solids of 30% by weight, and a concentration of thetotal solids of the fine resin particles in the recording liquid of 28%by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.7.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 55 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery hereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-5

Thirty-four parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 27parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), 19 parts by weight ofa resin dispersion containing water and fine fluorine-containing vinylether resin particles (average particle size: 0.15 μm) prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers (solidcontent: 50%, trade name: FE-3000, manufactured by Asahi Glass Co.,Ltd.), and 31 parts by weight of a resin dispersion containing water andfine modified polyester resin particles having carboxyl groups at sidechains (average particle size: 0.1 μm to 0.2 μm) (solid content: 30%,trade name: A-215G, manufactured by Takamatsu Yushi Co.) were uniformlymixed by stirring. Then, the resulting mixed liquid was filtered througha membrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 11% by weight, apigment (colorant) concentration in the solids of 30% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 25% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 60 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-6

Thirty-four parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 27parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), 19 parts by weight ofa resin dispersion containing water and fine fluorine-containing vinylether resin particles (average particle size: 0.15 μm) prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers (solidcontent: 50%, trade name: FE-3000, manufactured by Asahi Glass Co.,Ltd.), and 19 parts by weight of a resin dispersion containing water andfine modified styrene-butadiene copolymer resin particles (averageparticle size: 0.19 μm) (solid content: 48.5%, trade name: SN-335,manufactured by Sumika ABS Latex Co.) were uniformly mixed by stirring.Then, the resulting mixed liquid was filtered through a membrane filterhaving a pore size of 10 μm to remove dust and coarse particles, tothereby obtain a recording liquid having a pigment (colorant)concentration in the recording liquid of 13% by weight, a pigment(colorant) concentration in the solids of 30% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 28% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.7.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 55 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-7

Thirty-one parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 24parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), 28 parts by weight ofa resin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 30%, trade name: A-215G, manufacturedby Takamatsu Yushi Co.) and 17 parts by weight of a resin dispersioncontaining water and fine modified styrene-butadiene copolymer resinparticles (average particle size: 0.19 μm) (solid content: 48.5%, tradename: SN-335, manufactured by Sumika ABS Latex Co.) were uniformly mixedby stirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 11% by weight, apigment (colorant) concentration in the solids of 30% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 25% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 60 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-8

Thirty-two parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 19parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), 13 parts by weight ofa resin dispersion containing water and fine fluorine-containing vinylether resin particles (average particle size: 0.15 μm) prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers (solidcontent: 50%, trade name: FE-3000, manufactured by Asahi Glass Co.,Ltd.), 15 parts by weight of a resin dispersion containing water andfine silicon-modified acrylic resin particles (average particle size:0.1 μm to 0.2 μm) (solid content: 45%, trade name: G-45, manufactured bySanyo Chemical Industries, Ltd.), and 22 parts by weight of a resindispersion containing water and fine modified polyester resin particleshaving carboxyl groups at side chains (average particle size: 0.1 μm to0.2 μm) (solid content: 30%, trade name: A-215G, manufactured byTakamatsu Yushi Co.) were uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 11% by weight, a pigment (colorant)concentration in the solids of 30% by weight, and a concentration of thetotal solids of the fine resin particles in the recording liquid of 26%by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 80 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-9

Thirty-one parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 12parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), 8 parts by weight of aresin dispersion containing water and fine fluorine-containing vinylether resin particles (average particle size: 0.15 μm) prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers (solidcontent: 50%, trade name: FE-3000, manufactured by Asahi Glass Co.,Ltd.), 9 parts by weight of a resin dispersion containing water and finesilicon-modified acrylic resin particles (average particle size: 0.1 μmto 0.2 μm) (solid content: 45%, trade name: G-45, manufactured by SanyoChemical Industries, Ltd.), 14 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 30%, trade name: A-215G, manufactured by Takamatsu YushiCo.), 17 parts by weight of a resin dispersion containing water and finemodified polyester resin particles having carboxyl groups at side chains(average particle size: 0.1 μm to 0.2 μm) (solid content: 25%, tradename: A-115G, different from A-215G in pH and glass transitiontemperature, manufactured by Takamatsu Yushi Co.), and 9 parts by weightof a resin dispersion containing water and fine modifiedstyrene-butadiene copolymer resin particles (average particle size: 0.19μm) (solid content: 48.5%, trade name: SN-335, manufactured by SumikaABS Latex Co.) were uniformly mixed by stirring. Then, the resultingmixed liquid was filtered through a membrane filter having a pore sizeof 10 μm to remove dust and coarse particles, to thereby obtain arecording liquid having a pigment (colorant) concentration in therecording liquid of 11% by weight, a pigment (colorant) concentration inthe solids of 30% by weight, and a concentration of the total solids ofthe fine resin particles in the recording liquid of 25% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 110 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-10

Fourteen parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), 10 parts by weight ofa resin dispersion containing water and fine fluorine-containing vinylether resin particles (average particle size: 0.15 μm) prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers (solidcontent: 50%, trade name: FE-3000, manufactured by Asahi Glass Co.,Ltd.), and 11 parts by weight of a resin dispersion containing water andfine silicon-modified acrylic resin particles (average particle size:0.1 μm to 0.2 μm) (solid content: 45%, trade name: G-45, manufactured bySanyo Chemical Industries, Ltd.) were added to 64 parts by weight of anaqueous solution of a phthalocyanine dye (Acid Blue 9) (solid content:10%), and uniformly mixed by stirring. Then, the resulting mixed liquidwas filtered through a membrane filter having a pore size of 10 μm toremove dust and coarse particles, to thereby obtain a recording liquidhaving a dye (colorant) concentration in the recording liquid of 6% byweight, a dye (colorant) concentration in the solids of 30% by weight,and a concentration of the total solids of the fine resin particles inthe recording liquid of 15% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.8.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 60 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-11

Seven parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.), 5 parts by weight of aresin dispersion containing water and fine fluorine-containing vinylether resin particles, (average particle size: 0.15 μm) prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers (solidcontent: 50%, trade name: FE-3000, manufactured by Asahi Glass Co.,Ltd.), 5 parts by weight of a resin dispersion containing water and finesilicon-modified acrylic resin particles (average particle size: 0.1 μmto 0.2 μm) (solid content: 45%, trade name: G-45, manufactured by SanyoChemical Industries, Ltd.), 8 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 30%, trade name: A-215G, manufactured by Takamatsu YushiCo.), 10 parts by weight of a resin dispersion containing water and finemodified polyester resin particles having carboxyl groups at side chains(average particle size: 0.1 μm to 0.2 μm) (solid content: 25%, tradename: A-115G, manufactured by Takamatsu Yushi Co.), and 5 parts byweight of a resin dispersion containing water and fine modifiedstyrene-butadiene copolymer resin particles (average particle size: 0.19μm) (solid content: 48.5%, trade name: SN-335, manufactured by SumikaABS Latex Co.) were added to 61 parts by weight of an aqueous solutionof a phthalocyanine dye (Acid Blue 9) (solid content: 10%), anduniformly mixed by stirring. Then, the resulting mixed liquid wasfiltered through a membrane filter having a pore size of 10 μm to removedust and coarse particles, to thereby obtain a recording liquid having adye (colorant) concentration in the recording liquid of 6% by weight, adye (colorant) concentration in the solids of 30% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 14% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried. at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density. of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.8.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 1-1. As aresult, according to this system, the allowance time until developmentof the clogging with the recording liquid was as long as 115 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 1-12

Thirty-one parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 43parts by weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.), and 26 parts by weight ofa resin dispersion containing water and fine fluorine-containing vinylether resin particles (average particle size: 0.15 μm) prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers (solidcontent: 50%, trade name: FE-3000, manufactured by Asahi Glass Co., Ltd.were uniformly mixed by stirring. Then, the resulting mixed liquid wasfiltered through a membrane filter having a pore size of 11 μm to removedust and coarse particles, to thereby obtain a recording liquid having apigment (colorant) concentration in the recording liquid of 11% byweight, a pigment (colorant) concentration in the solids of 30% byweight, and a concentration of the total solids of the fine resinparticles in the recording liquid of 26% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 1-1 to 1-11. As aresult, the allowance time until development of clogging was 40 seconds,and an original fluid of the recording liquid not diluted with watercould be stably discharged by use of the commercial ink jet printer. Thesolid image formed by application of the recording liquid in a smallamount of 0.9 mg per cm² of image area showed an optical density of 1.3.

Comparative Example 1-1

Thirty parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%) and 70parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.) were uniformly mixed bystirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 10% by weight, apigment (colorant) concentration in the solids of 30% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 25% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 1-1 to 1-11. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.6. However, the allowance time until development of clogging was asshort as 8 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density as low as 0.6.

Comparative Example 1-2

Thirty-eight parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%) and 62parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.) were uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 13% by weight, a pigment (colorant)concentration in the solids of 30% by weight, and a concentration of thetotal solids of the fine resin particles in the recording liquid of 31%by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 1-1 to 1-11. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of the cloggingwas as short as 10 seconds. Further, as a result of the printing testwith the commercial ink jet printer, clogging developed, and it wasimpossible to stably discharge an original fluid of the recording liquidnot diluted with water.

This recording liquid was diluted 4 times with distilled water. As aresult, it became dischargeable with the commercial ink jet printer.However, the solid image formed by application of the recording liquidin a small amount of 0.9 mg per cm² of image area showed an opticaldensity as low as 0.5.

Comparative Example 1-3

Twenty-seven parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%) and 73parts by weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.) were uniformly mixed bystirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 9% by weight, apigment (colorant) concentration in the solids of 30% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 22% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 1-1 to 1-11. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was asshort as 12 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times with distilled water. As aresult, it became dischargeable with the commercial ink jet printer.However, the solid image formed by application of the recording liquidin a small amount of 0.9 mg per cm² of image area showed an opticaldensity as low as 0.5.

Comparative Example 1-4

Thirty-five parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%) and 65parts by weight of a resin dispersion containing water and finesilicon-modified acrylic resin particles (average particle size: 0.1 μmto 0.2 μm) (solid content: 45%, trade name: G-45, manufactured by SanyoChemical Industries, Ltd.) were uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 12% by weight, a pigment (colorant)concentration in the solids of 30% by weight, and a concentration of thetotal solids of the fine resin particles in the recording liquid of 29%by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 1-1 to 1-11. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was asshort as 10 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times with distilled water. As aresult, it became dischargeable with the commercial ink jet printer.However, the solid image formed by application of the recording liquidin a small amount of 0.9 mg per cm² of image area showed an opticaldensity as low as 0.6.

Comparative Example 1-5

Thirty-seven parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%) and 63parts by weight of a resin dispersion containing water and fine modifiedstyrene-butadiene copolymer resin particles (average particle size: 0.19μm) (solid content: 48.5%, trade name: SN-335, manufactured by SumikaABS Latex Co.) were uniformly mixed by stirring. Then, the resultingmixed liquid was filtered through a membrane filter having a pore sizeof 10 μm to remove dust and coarse particles, to thereby obtain arecording liquid having a pigment (colorant) concentration in therecording liquid of 13% by weight, a pigment (colorant) concentration inthe solid of 30% by weight, and a concentration of the total solids ofthe fine resin particles in the recording liquid of 31% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 1-1 to 1-11. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.3. However, the allowance time until development of clogging was asshort as 10 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times with distilled water. As aresult, it became dischargeable with the commercial ink jet printer.However, the solid image formed by application of the recording liquidin a small amount of 0.9 mg per cm² of image area showed an opticaldensity as low as 0.6.

Comparative Example 1-6

Forty parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.) was added to 60 partsby weight of an aqueous solution of a phthalocyanine dye (Acid Blue 9)(solid content: 10%), and uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 6% by weight, a pigment (colorant) concentrationin the solids of 30% by weight, and a concentration of the total solidsof the fine resin particles in the recording liquid of 14% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 1-1 to 1-11. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.6. However, the allowance time until development of clogging was asshort as 10 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times with distilled water. As aresult, it became dischargeable with the commercial ink jet printer.However, the solid image formed by application of the recording liquidin a small amount of 0.9 mg per cm² of image area showed an opticaldensity as low as 0.6.

Comparative Example 1-7 to 1-10

Recording liquids were prepared and tested in the same manner as inComparative Example 1-6, except that the resin dispersion containingwater and fine acrylsilicone resin particles having methoxysilyl groupswas substituted by the resin dispersions used in Comparative Examples1-2 to 1-5, respectively. As a result, in all combinations each usingonly one kind of fine resin particles, high optical density could not beattained compatible with the prevention of clogging.

As described above, in all the recording liquids of Examples 1-1 to1-11, high optical density could be attained compatible with theprevention of clogging, different from Comparative Examples.

EXAMPLE 2-1

A recording liquid was prepared as follows. Twenty-two parts by weightof an aqueous dispersion of a copper phthalocyanine pigment (PigmentBlue 15:3) (solid content: 35%), 21 parts by weight of a resindispersion containing water and fine fluorine-containing vinyl etherresin particles (average particle size: 0.15 μm) prepared by emulsionpolymerization of fluoroolefin and vinyl ether monomers (solid content:50%, trade name: FE-3000, manufactured by Asahi Glass Co., Ltd.), 23parts by weight of a resin dispersion containing water and finesilicon-modified acrylic resin particles (average particle size: 0.1 μmto 0.2 μm) (solid. content: 45%, trade name: G-45, manufactured by SanyoChemical Industries, Ltd.), and 34 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 30%, trade name: A-215G, manufactured by Takamatsu YushiCo.) were uniformly mixed by stirring. Then, the resulting mixed liquidwas filtered through a membrane filter having a pore size of 10 μm toremove dust and coarse particles, to thereby obtain a recording liquidhaving a pigment (colorant) concentration in the recording liquid {(thepigment solid amount×100)/the total amount of the recording liquid} of8% by weight, a pigment (colorant) concentration in the solids {(thepigment solid amount×100)/the sum of the pigment solid amount and thetotal amount of fine resin particle solids} of 20% by weight, and aconcentration of the total amount of the fine resin particle solids inthe recording liquid {(the total amount of the fine resin particlesolids×100)/the total amount of the recording liquid} of 31% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,to thereby obtain a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.4.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

On the other hand, clogging with the recording liquid at a dischargeoutlet of a recording head was evaluated in the following manner. Astandard injection needle having an inner diameter of 180 μm(manufactured by Iwashita Engineering Co.) was set on a tip of aninjector having an inner diameter of 15 mm, and 10 ml of the recordingliquid was sucked in this injector. Then, the injector was allowed tostand in a state in which dropping of the recording liquid from theneedle was stopped by sealing an upper portion of the injector. After anelapse of a specified time, the upper portion was opened, and it wasobserved whether the recording liquid could be continuously dropped fromthe needle. This operation was repeated while prolonging the specifiedtime of standing little by little, and the longest time of standinguntil which the recording liquid could be dropped from the needle wastaken as the allowance time until development of the clogging. Accordingto this system, the thus-measured allowance time until development ofthe clogging with the recording liquid was as long as 50 seconds.

Then, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Further, water was spilled on the above described solid image formedwith a bar coater and the print sample obtained by use of the printer toevaluate the water resistance. As a result, blurring of the image andextension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-2

Twenty-two parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 20parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), 20 parts by weight of a resin dispersioncontaining water and fine modified styrene-butadiene copolymer resinparticles (average particle size: 0.19 μm) (solid content: 48.5%, tradename: SN-335, manufactured by Sumika ABS Latex Co.), and 39 parts byweight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 25%, trade name:A-115G, different from A-215G in pH and glass transition temperature,manufactured by Takamatsu Yushi Co.) were uniformly mixed by stirring.Then, the resulting mixed liquid was filtered through a membrane filterhaving a pore size of 10 μm to remove dust and coarse particles, tothereby obtain a recording liquid having a pigment (colorant)concentration in the recording liquid of 7% by weight, a pigment(colorant) concentration in the solids of 20% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 29% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.4.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 2-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 50 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-3

Twenty-three parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 16parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), 18 parts by weight of a resin dispersioncontaining water and fine silicon-modified acrylic resin particles(average particle size: 0.1 μm to 0.2 μm) (solid content: 45%, tradename: G-45, manufactured by Sanyo Chemical Industries, Ltd.), 27 partsby weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.), and 17 parts by weight ofa resin dispersion containing water and fine modified styrene-butadienecopolymer resin particles (average particle size: 0.19 μm) (solidcontent: 48.5%, trade name: SN-335, manufactured by Sumika ABS LatexCo.) were uniformly mixed by stirring. Then, the resulting mixed liquidwas filtered through a membrane filter having a pore size of 10 μm toremove dust and coarse particles, to thereby obtain a recording liquidhaving a pigment (colorant) concentration in the recording liquid of 8%by weight, a pigment (colorant) concentration in the solids of 20% byweight, and a concentration of the total solids of the fine resinparticles in the recording liquid of 32% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 2-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 100 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-4

Twenty parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 14parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), 15 parts by weight of a resin dispersioncontaining water and fine modified styrene-butadiene copolymer resinparticles (average particle size: 0.19 μm) (solid content: 48.5%, tradename: SN-335, manufactured by Sumika ABS Latex Co.), 23 parts by weightof a resin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 30%, trade name: A-215G, manufacturedby Takamatsu Yushi Co.), and 28 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 25%, trade name: A-115G, manufactured by Takamatsu YushiCo.) were uniformly mixed by stirring. Then, the resulting mixed liquidwas filtered through a membrane filter having a pore size of 10 μm toremove dust and coarse particles, to thereby obtain a recording liquidhaving a pigment (colorant) concentration in the recording liquid of 7%by weight, a pigment (colorant) concentration in the solids of 20% byweight, and a concentration of the total solids of the fine resinparticles in the recording liquid of 28% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.5.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 2-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 105 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-5

Twenty parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 15parts by weight of a resin dispersion containing water and finesilicon-modified acrylic resin particles (average particle size: 0.1 μmto 0.2 μm) (solid content: 45%, trade name: G-45, manufactured by SanyoChemical Industries, Ltd.), 14 parts by weight of a resin dispersioncontaining water and fine modified styrene-butadiene copolymer resinparticles (average particle size: 0.19 μm) (solid content: 48.5%, tradename: SN-335, manufactured by Sumika ABS Latex Co.), 23 parts by weightof a resin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 30%, trade name: A-215G, manufacturedby Takamatsu Yushi Co.), and 28 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 25%, trade name: A-115G, manufactured by Takamatsu YushiCo.) were uniformly mixed by stirring. Then, the resulting mixed liquidwas filtered through a membrane filter having a pore size of 10 μm toremove dust and coarse particles, to thereby obtain a recording liquidhaving a pigment (colorant) concentration in the recording liquid of 7%by weight, a pigment (colorant) concentration in the solids of 20% byweight, and a concentration of the total solids of the fine resinparticles in the recording liquid of 28% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.4.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 2-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 90 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-6

Twenty-one parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 12parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), 13 parts by weight of a resin dispersioncontaining water and fine silicon-modified acrylic resin particles(average particle size: 0.1 μm to 0.2 μm) (solid content: 45%, tradename: G-45, manufactured by Sanyo Chemical Industries, Ltd.), 19 partsby weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.), 23 parts by weight of aresin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 25%, trade name: A-115G, manufacturedby Takamatsu Yushi Co.), and 12 parts by weight of a resin dispersioncontaining water and fine modified styrene-butadiene copolymer resinparticles (average particle size: 0.19 μm) (solid content: 48.5%, tradename: SN-335, manufactured by Sumika ABS Latex Co.) were uniformly mixedby stirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 7% by weight, apigment (colorant) concentration in the solids of 20% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 29% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope.. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 2-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 135 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled,on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-7

Twenty-one parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 10parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), 11 parts by weight of a resin dispersioncontaining water and fine silicon-modified acrylic resin particles(average particle size: 0.1 μm to 0.2 μm) (solid content: 45%, tradename: G-45, manufactured by Sanyo Chemical Industries, Ltd.), 16 partsby weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.), 19 parts by weight of aresin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 25%, trade name: A-115G, manufacturedby Takamatsu Yushi Co.), 10 parts by weight of a resin dispersioncontaining water and fine modified styrene-butadiene copolymer resinparticles (average particle size: 0.19 μm) (solid content: 48.5%, tradename: SN-335, manufactured by Sumika ABS Latex Co.), and 14 parts byweight of a resin dispersion containing water and fine acrylsiliconeresin particles (average particle size: 0.1 μm to 0.2 μm) havingmethoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.) were uniformly mixed bystirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 7% by weight, apigment (colorant) concentration in the solids of 20% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 29% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 2-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 170 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-8

Twenty parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 7 partsby weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), 8 parts by weight of a resin dispersioncontaining water and fine silicon-modified acrylic resin particles(average particle size: 0.1 μm to 0.2 μm) (solid content: 45%, tradename: G-45, manufactured by Sanyo Chemical Industries, Ltd.), 12 partsby weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.), 14 parts by weight of aresin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 25%, trade name: A-115G, manufacturedby Takamatsu Yushi Co.), 12 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 30%, trade name: A-515G, different from A-215G andA-115G in pH and glass transition temperature, manufactured by TakamatsuYushi Co.), 7 parts by weight of a resin dispersion containing water andfine modified styrene-butadiene copolymer resin particles (averageparticle size: 0.19 μm) (solid content: 48.5%, trade name: SN-335,manufactured by Sumika ABS Latex Co.), 9 parts by weight of a resindispersion containing water and fine acrylate-silicone copolymer resinparticles (average particle size: 0.16 μm) (solid content: 38.8%, tradename: ROY-6312, manufactured by Showa Highpolymer Co., Ltd.), and 10parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.) were uniformly mixed bystirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 7% by weight, apigment (colorant) concentration in the solids of 20% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 28% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.6.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 2-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 195 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-9

Six parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), 7 parts by weight of a resin dispersioncontaining water and fine silicon-modified acrylic resin particles(average particle size: 0.1 μm to 0.2 μm) (solid content: 45%, tradename: G-45, manufactured by Sanyo Chemical Industries, Ltd.), 11 partsby weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.), 13 parts by weight of aresin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 25%, trade name: A-115G, manufacturedby Takamatsu Yushi Co.), 7 parts by weight of a resin dispersioncontaining water and fine modified styrene-butadiene copolymer resinparticles (average particle size: 0.19 μm) (solid content: 48.5%, tradename: SN-335, manufactured by Sumika ABS Latex Co.), and 9 parts byweight of a resin dispersion containing water and fine acrylsiliconeresin particles (average particle size: 0.1 μm to 0.2 μm) havingmethoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.) were added to 48 partsby weight of an aqueous solution of a phthalocyanine dye (Acid Blue 9)(solid content: 10%), and uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording. liquid having a dye (colorant) concentration in therecording liquid of 5% by weight, a dye (colorant) concentration in thesolids of 20% by weight, and a concentration of the total solids of thefine resin particles in the recording liquid of 19% by weight.

The recording liquid thus prepared was applied onto plain paper forcopying machines by use of a bar coater, and dried at room temperature,thereby obtaining a solid image composed of a dry coated film on theplain paper. The optical density of the resulting image was measuredfrom the surface side of the image. As a result, the solid image formedby application of the recording liquid in a small amount of 0.9 mg percm² of image area showed an optical density as high as 1.4.

Further, a longitudinal section of the solid image on the plain paperwas observed under an optical microscope. As a result, the solid imagewas mainly formed on the plain paper, and no substantial penetration ofthe recording liquid in the plain paper was observed.

Then, clogging with the. recording liquid at a discharge outlet of arecording head was evaluated in the same manner as in Example 2-1. As aresult, according to this system, the allowance time until developmentof clogging with the recording liquid was as long as 180 seconds.

Further, the printing test of this recording liquid on plain paper wascarried out by use of a commercial ink jet printer. As a result, anoriginal fluid of the recording liquid not diluted with water could bestably discharged. The observation of print dots of a thus-printedsample under a magnifying glass and an optical microscope revealed thatthe dots were distinct without blurring in the periphery thereof.

Subsequently, water was spilled on the above described solid imageformed with a bar coater and the print. sample obtained by use of theprinter to evaluate water resistance. As a result, blurring of the imageand extension of the colorant caused by water were not observed, whichproved that the recording liquid of this example had high waterresistance.

EXAMPLE 2-10

Twenty-one parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 30parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), and 49 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 30%, trade name: A-215G, manufactured by Takamatsu YushiCo.) were uniformly mixed by stirring. Then, the resulting mixed liquidwas filtered through a membrane filter having a pore size of 10 μm toremove dust and coarse particles, to thereby obtain a recording liquidhaving a pigment (colorant) concentration in the recording liquid of 7%by weight, a pigment (colorant) concentration in the solids of 20% byweight, and a concentration of the total solids of the fine resinparticles in the recording liquid of 30% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was 20seconds. Further, as a result of the printing test with the commercialink jet printer, clogging developed, and it was impossible to stablydischarge an original fluid of the recording liquid not diluted withwater.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density of 0.4.

EXAMPLE 2-11

Nineteen parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 30parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), and 54 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 25%, trade name: A-115G, manufactured by Takamatsu YushiCo.) were uniformly mixed by stirring. Then, the resulting mixed liquidwas filtered through a membrane filter having a pore size of 10 μm toremove dust and coarse particles, to thereby obtain a recording liquidhaving a pigment colorant) concentration in the recording liquid of 7%by weight, a pigment (colorant) concentration in the solids of 20% byweight, and a concentration of the total solids of the fine resinparticles in the recording liquid of 27% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was 20seconds. Further, as a result of the printing test with the commercialink jet printer, clogging developed, and it was impossible to stablydischarge an original fluid of the recording liquid not diluted withwater.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per. cm²of image area showed an optical density of 0.4.

EXAMPLE 2-12

Twenty-one parts by weight of an aqueous dispersion of d copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 30parts by weight of a resin dispersion containing water and fine modifiedstyrene-butadiene copolymer resin particles (average particle size: 0.19μm) (solid content: 48.5%, trade name: SN-335, manufactured by SumikaABS Latex Co.), and 49 parts by weight of a resin dispersion containingwater and fine modified polyester resin particles having carboxyl groupsat side chains (average particle size: 0.1 μm to 0.2 μm) (solid content:30%, trade name: A-215G, manufactured by Takamatsu Yushi Co.) wereuniformly mixed by stirring. Then, the resulting mixed liquid wasfiltered through a membrane filter having a pore size of 10 μm to removedust and coarse particles, to thereby obtain a recording liquid having apigment (colorant) concentration in the recording liquid of 7% byweight, a pigment (colorant) concentration in the solids of 20% byweight, and a concentration of the total solids of the fine resinparticles in the recording liquid of 29% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was 18seconds. Further, as a result of the printing test with the commercialink jet printer, clogging developed, and it was impossible to stablydischarge an original fluid of the recording liquid not diluted withwater.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density of 0.4.

EXAMPLE 2-13

Nineteen parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), 30parts by weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.), and 54 parts by weight ofa resin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 25%, trade name: A-115G, manufacturedby Takamatsu Yushi Co.) were uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 7% by weight, a pigment (colorant) concentrationin the solids of 20% by weight, and a concentration of the total solidsof the fine resin particles in the recording liquid of 27% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.3. However, the allowance time until development of clogging was 20seconds. Further, as. a result of the printing test with the commercialink jet printer, clogging developed, and it was impossible to stablydischarge an original fluid of the recording liquid not diluted withwater.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density of 0.3.

EXAMPLE 2-14

Nineteen parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.), and 32 parts by weight of a resin dispersioncontaining water and fine modified polyester resin particles havingcarboxyl groups at side chains (average particle size: 0.1 μm to 0.2 μm)(solid content: 30%, trade name: A-215G, manufactured by Takamatsu YushiCo.) was added to 48 parts by weight of an aqueous solution of aphthalocyanine dye (Acid Blue 9) (solid content: 10%), and uniformlymixed by stirring. Then, the resulting mixed liquid was filtered througha membrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a dye (colorant)concentration in the recording liquid of 5% by weight, a dye (colorant)concentration in the solids of 20% by weight, and a concentration of thetotal solids of the fine resin particles in the recording liquid of 19%by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was 22seconds. Further, as a result of the printing test with the commercialink jet printer, clogging developed, and it was impossible to stablydischarge an original fluid of the recording liquid not diluted withwater.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density of 0.3.

EXAMPLE 2-15

A recording liquid was prepared and tested in the same manner as inExample 2-14, except that the resin dispersion containing water and finemodified polyester resin particles having carboxyl groups at side chains(trade name: A-215G, manufactured by Takamatsu Yushi Co.) wassubstituted by a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 25%, trade name:A-115G, manufactured by Takamatsu Yushi Co.). As a result, high opticaldensity could not attained compatible with the prevention of clogging.

EXAMPLE 2-16

A recording liquid was prepared and tested in the same manner as inExample 2-14, except that the resin dispersion containing water and finefluorine-containing vinyl ether resin particles prepared by emulsionpolymerization of fluoroolefin and vinyl ether monomers was substitutedby a resin dispersion containing water and fine modifiedstyrene-butadiene copolymer resin particles (average particle size: 0.19μm) (solid content: 48.5%, trade name: SN-335, manufactured by SumikaABS Latex Co.). As a result, high optical density could not be attainedcompatible with the prevention of clogging.

EXAMPLE 2-17

A recording liquid was prepared and tested in the same manner as inExample 14, except that the resin dispersion. containing water and finefluorine-containing vinyl ether resin particles prepared by emulsionpolymerization of fluoroolefin and vinyl ether monomers was substitutedby a resin dispersion containing water and fine modified polyester resinparticles having carboxyl groups at side chains (average particle size:0.1 μm to 0.2 μm) (solid content: 30%, trade name: A-215G, manufacturedby Takamatsu Yushi Co.), and that the resin dispersion containing waterand fine modified polyester resin particles having carboxyl groups atside chains (trade name: A-215G, manufactured by Takamatsu Yushi Co.)was substituted by a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 25%, trade name:A-115G, manufactured by Takamatsu Yushi Co.). As a result, high opticaldensity could not be attained compatible with the prevention ofclogging.

Comparative Example 2-1

Twenty-six parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), and 74parts by weight of a resin dispersion containing water and finefluorine-containing vinyl ether resin particles (average particle size:0.15 μm) prepared by emulsion polymerization of fluoroolefin and vinylether monomers (solid content: 50%, trade name: FE-3000, manufactured byAsahi Glass Co., Ltd.) were uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 9% by weight, a pigment (colorant) concentrationin the solids of 20% by weight, and a concentration of the total solidsof the fine resin particles in the recording liquid of 37% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was asshort as 8 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density as low as 0.4.

Comparative Example 2-2

Twenty-four parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), and 76parts by weight of a resin dispersion containing water and finesilicon-modified acrylic resin particles (average particle size: 0.1 μmto 0.2 μm) (solid content: 45%, trade name: G-45, manufactured by SanyoChemical Industries, Ltd.) were uniformly mixed by stirring. Then, theresulting mixed liquid was filtered through a membrane filter having apore size of 10 μm to remove dust and coarse particles, to therebyobtain a recording liquid having a pigment (colorant) concentration inthe recording liquid of 9% by weight, a pigment (colorant) concentrationin the solids of 20% by weight, and a concentration of the total solidsof the fine resin particles in the recording liquid of 34% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.3. However, the allowance time until development of clogging was asshort as 10 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density as low as 0.4.

Comparative Example 2-3

Eighteen parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), and 82parts by weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 30%, trade name:A-215G, manufactured by Takamatsu Yushi Co.) were uniformly mixed bystirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to. remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 6% by weight, apigment (colorant) concentration in the solids of 20% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 25% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.2. However, the allowance time until development of clogging was asshort as 10 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density as low as 0.4.

Comparative Example 2-4

Twenty-six parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), and 74parts by weight of a resin dispersion containing water and fine modifiedstyrene-butadiene copolymer resin particles (average particle size: 0.19μm) (solid content: 48.5%, trade name: SN-335, manufactured by SumikaABS Latex Co.) were uniformly mixed by stirring. Then, the resultingmixed liquid was filtered through a membrane filter having a pore sizeof 10 μm to remove dust and coarse particles, to thereby obtain arecording liquid having a pigment (colorant) concentration in therecording liquid of 9% by weight, a pigment (colorant) concentration inthe solids of 20% by weight, and a concentration of the total solids ofthe fine resin particles in the recording liquid of 36% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was asshort as 8 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density as low as 0.4.

Comparative Example 2-5

Fifteen parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), and 85parts by weight of a resin dispersion containing water and fine modifiedpolyester resin particles having carboxyl groups at side chains (averageparticle size: 0.1 μm to 0.2 μm) (solid content: 25%, trade name:A-115G, manufactured by Takamatsu Yushi Co.) were uniformly mixed bystirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 5% by weight, apigment (colorant) concentration in the solids of 20% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 21% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.2. However, the allowance time until development of clogging was asshort as 10 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density as low as 0.4.

Comparative Example 2-6

Twenty parts by weight of an aqueous dispersion of a copperphthalocyanine pigment (Pigment Blue 15:3) (solid content: 35%), and 80parts by weight of a resin dispersion containing water and fineacrylsilicone resin particles (average particle size: 0.1 μm to 0.2 μm)having methoxysilyl groups (solid content: 35%, trade name: SW-135,manufactured by Sanyo Chemical Industries, Ltd.) were uniformly mixed bystirring. Then, the resulting mixed liquid was filtered through amembrane filter having a pore size of 10 μm to remove dust and coarseparticles, to thereby obtain a recording liquid having a pigment(colorant) concentration in the recording liquid of 7% by weight, apigment (colorant) concentration in the solids of 20% by weight, and aconcentration of the total solids of the fine resin particles in therecording liquid of 28% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was asshort as 7 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density as low as 0.5.

Comparative Example 2-7

Forty-four parts by weight of a resin dispersion containing water andfine fluorine-containing vinyl ether resin particles (average particlesize: 0.15 μm) prepared by emulsion polymerization of fluoroolefin andvinyl ether monomers (solid content: 50%, trade name: FE-3000,manufactured by Asahi Glass Co., Ltd.) was added to 56 parts by weightof an aqueous solution of a phthalocyanine dye (Acid Blue 9) (solidcontent: 10%), and uniformly mixed by stirring. Then, the resultingmixed liquid was filtered through a membrane filter having a pore sizeof 10 μm to remove dust and coarse particles, to thereby obtain arecording liquid having a dye (colorant) concentration in the recordingliquid of 6% by weight, a dye (colorant) concentration in the solids of20% by weight, and a concentration of the total solids of the fine resinparticles in the recording liquid of 22% by weight.

For the recording liquid thus prepared, the measurement of the opticaldensity, the measurement of the allowance time until development ofclogging, and the printing test on plain paper with a commercial ink jetprinter were made in the same manner as in Examples 2-1 to 2-9. As aresult, the solid image formed by application of the recording liquid ina small amount of 0.9 mg per cm² of image area showed an optical densityof 1.4. However, the allowance time until development of clogging was asshort as 10 seconds. Further, as a result of the printing test with thecommercial ink jet printer, clogging developed, and it was impossible tostably discharge an original fluid of the recording liquid not dilutedwith water.

This recording liquid was diluted 4 times (recording liquid:water=1:3)with distilled water. As a result, it became dischargeable with thecommercial ink jet printer. However, the solid image formed byapplication of the recording liquid in a small amount of 0.9 mg per cm²of image area showed an optical density as low as 0.3.

Comparative Example 2-8 to 2-12

Recording liquids were prepared and tested in the same manner as inComparative Example 2-7, except that the resin dispersion containingfine fluorine-containing vinyl ether resin particles prepared byemulsion polymerization of fluoroolefin and vinyl ether monomers wassubstituted by the resin dispersions used in Comparative Examples 2-2 to2-6, respectively. As a result, in all combinations each using only onekind of fine resin particles, high optical density could not be attainedcompatible with the prevention of clogging.

As demonstrated above, the recording liquid of the present inventionprovides an image having high image density, exhibiting no blurring onrecording paper and no penetration therein, and excellent in waterresistance, and has excellent discharge stability.

While the invention has been described in detail and with reference tospecific examples thereof, it will be apparent to one skilled in the artthat various changes and modifications can be made therein withoutdeparting from spirit and scope thereof.

What is claimed is:
 1. An image recording method comprising dischargingdroplets of a recording ink from discharge outlet sections of arecording head and placing the ink droplets on a recording medium toform an image thereon, said recording ink comprising a colorant, waterand at least two kinds of resin particles each having an averageparticle size of from 0.01 μm to 5 μm, wherein at least one of said atleast two kinds of resin particles are self-crosslinkable resinparticles.
 2. The image recording method according to claim 1, whereinthe number of the kinds of said resin particles is 3 or more.
 3. Theimage recording method according to claim 1, wherein the number of thekinds of said resin particles is 4 or more.
 4. The image recordingmethod according to claim 1, wherein said recording medium is plainpaper.
 5. The image recording method according to claim 1, wherein thedroplets are discharged from ink jet nozzles, and wherein said at leasttwo kinds of resin particles comprise first resin particles and asufficient amount of second resin particles for reducing agglomerationof the first resin particles and the second resin particles in thenozzles.
 6. The image recording method according to claim 5, wherein thefirst resin particles and the second resin particles are totallyintroduced in the water in amounts sufficient to increase thewater-repellency of the colorant.
 7. The image recording methodaccording to claim 1, wherein said ink contains non-crosslinkable resinparticles.
 8. The image recording method according to claim 1, whereinsaid self-crosslinkable resin particles are acrylsilicone resinparticles.
 9. The image recording method according to claim 8, whereinsaid acrylsilicone resin particles contain an alkoxysilyl group.
 10. Theimage recording method according to claim 7, wherein saidnon-crosslinkable resin particles are fluororesin particles.
 11. Theimage recording method according to claim 10, wherein said fluororesinparticles have fluoroolefin units.
 12. The image recording methodaccording to claim 1, wherein the total content of said resin particlesin the recording ink is from 10 to 95% by weight.
 13. The imagerecording method according to claim 1, wherein said colorant is apigment.
 14. The image recording method according to claim 13, whereinthe content of said pigment in the recording ink is from 1 to 50% byweight.
 15. The image recording method according to claim 1, whereinsaid colorant is a dye.
 16. The image recording method according toclaim 15, wherein the content of said dye in the recording ink is from0.2 to 40% by weight.